Acrylates of nf2-containing polyethers



United States Patent 3,441,549 ACRYLATES OF NEE-CONTAINING POLYETHERS John B. Gardiner, Mountainside, and Anthony J. Passannante, Metuchen, N.J., assignors to Esso Research and Engineering Company, a corporation of Delaware N0 Drawing. Filed Sept. 11, 1962, Ser. No. 224,885 Int. Cl. C08f 3/64; C07c 135/00, 87/26 U.S. Cl. 260-883 14 Claims This invention relates to high-energy acrylate and polyacrylate binders containing NF oxidizing groups and their preparation from polyethers containing NF groups.

The high-energy oxidizer binders obtained from N1 containing polyether acrylates are demonstrated to have improved chemical and physical characteristics for use in solid rocket propellants which require in their formulation high-energy binders. Such binders in solid rocket propellants are employed in proportions of about 5 to 30 wt. percent of the composite to hold together other components dispersed in the binders, such as liquid oxidizers, solid oxidizers, and fuels such as powdered metals of the class comprising B, Al, Be Li and Mg, and compounds of such materials, e.g. their hydrides.

With advances in the art of preparing high-energy binders, it has been found that a number of properties of the binders should and can be improved, as, for example, the properties of stability in various liquid oxi dizers, flexibility and rubbery qualities, tensile strength, heat of polymerization, low sensitivity to impact, and energy content.

The new type of binder provided by the present invention is believed to make improvements in such properties as mentioned.

To make the high-energy polyether acrylates containing NF groups, the starting materials are polyethers having a suitable high content of NF groups and OH functionality. Some of the -NF -containing polyethers may be made by epoxidizing an NF -containing olefin and polymerizing the NF containing epoxide. The preferred NF -containing polyethers have been made by reacting N R, with unsaturated polyethers, e.g. reacting N F with poly (pentadiene monoxide) which is formed by ploymerizing pentadiene monoxide as described in an application of Anthony J. Passannante et al., S.N. 219,- 372, filed Aug. 22, 1962. Another exemplary NF -containing polyether is described in application S.N. 219,373 of Anthony J. Passannante et al., filed Aug. 22, 19 62.

The NF -containing polyethers are acrylated preferably with an excess of acrylating agent, such as acryloyl chloride, acrylic anhydride, arcylic acid, and other acrylating agents which may have substituents and which react with OH groups in the polyethers, which are termed NF polyether alcohols. The terms acrylates, polyacrylates, and acrylating agent are intended to include the alphasubstituted methyl and homologous modifications.

While a variety of steps may be involved in arriving at the final high-energy binder compositions, this invention is concerned in particular with the synthesis of acrylates suitable for compositing as prepolymers with loading of oxidizers and fuels before final polymerization or casting. The initial materials, insofar as the present invention is concerned, are the NF -polyether alco- 'ice hols which are to be acrylated, but a brief description will be given of the preferred method for making the NF polyether alcohols which are acrylated, and a description will be given of how the prepolymers, or polyether acrylates, are given a final polymerization to desired binder compositions.

PREPARATION OF NFg-POLYETHER ALCOHOLS In the preferred method of making an NF -polyether alcohol for acrylation, 1,4-pentadiene monoxide, having the formula is polymerized with an epoxide polymerization catalyst, such as PF in a proportion of 0.01 to 10% by weight at 20 to 25 C. for a period of 0.5 to 72 hours to obtain a polymer having a molecular weight in the range of about 500 to 5000 with terminal OH groups attached to the chain of recurring units. The OH functionality of the polyether may be controlled by using modifiers, such as glycidol, ethylene glycol, water, or trimethylol propane. The resulting unsaturated polyether reacts with N F; smoothly and an excess of N F is used in chloroform or other halogen-substituted alkane solution at to C. The resulting N 1 adduct of the unsaturated polyether contains NF groups attached to the carbons which were linked together by the double bond and this adduct, which may be termed poly (4,5-bis-(difluoramino)-pentene-l oxide), has the structural formula:

In this polyether, the recurring unit is present in a number n times, for example, 2 to 30. The number of OH groups on the chain depends on the method of terminating the chain and, generally, is an average of 1.5 to 2.5 or 3 OH groups per molecule, but may be higher.

A still higher energy NF -polyether alcohol is made by polymerizing divinyl ethylene oxide with an epoxide polymerization catalyst, preferably PF and reacting the resulting unsaturated polyether alcohol with N 1 to obtain the polymer poly (l,2,5,6-tetrakis-(difiuoramino)- heXene-3 oxide) represented as:

This polymer, having four NF groups per six carbon atoms in the recurring unit, also has OH groups terminating the chains.

ACRYLATION OF NF -POLYETHER ALCOHOLS Acrylation of the NF -polyether alcohols to form polymers that give satisfactory rubbery binders has been demonstrated as shown in the following example.

Example 1.-Acrylation of poly (bis-(NF pentene-l oxide) The reaction mixture components used were:

2.0 g. (.0017 mole) direct addition poly-bis-(NF pen tene oxide (mol. wt. 1170); 2.28 g. (.0253 mole) acryloyl chloride; ml. benzene-acetonitrile (SO-% vol.) solvent; .01 g. CuCl (anhydrous) inhibitor for acryloyl chlorlde polymerization.

The components were mixed under N for 2 hours at C. and then 1 hour at 50 C. The solvent and acryloyl chloride excess were removed under vacuum, giving an amber polymer (mol. wt. 1200) oil.

TABLE I.NFg-POLYACR YLATES FROM N2F4 ADDUCT OF POLYPENTA- DIENE MONOXIDE Ethylene Water Glycol Glyeidol Polyether Modified Modified Copolymer Molecular weight l, 266 1, 260 2, 389 OH/Ghain (via 13).. 1. 46 1.62 1. 79 IR Absorbance Ratio.

HO/CH-C'Hz .404 485 301 NFZ, wt. percent (N+F) 53.0 52. 7 49. 9 Derived Aerylate:

Acryloyl Chloride/Polyether (equivalents) 7/1 13/1 24/1 Appearance IR Absorbanee Ratioz C=O/CH-CH2 2.2 2.1 1.6 Derived Polyaerylates, Elemental Analyses:

NFQ, wt. percent (N+F) 53. 4 50. 4 51. 9

NFQ, wt. percent based on percent F 54. 8 51. 4 53. 6

Cl, wt. percent 1. 48 1.82 1. 53

1 Ratio of the absorbance peak heights at 2.8 (OH) and 5.814 (0 0) to 3.4 (CH-CH2) 2 Acrylation as described in the example given above.

5 Polymerized acrylate using 0.3 wt. percent azoisobutyronitrile (AIBN), N atmosphere, 50 0., for 15 hours for curing.

4 Amber syrup.-

5 Straw syrup.

The acrylate may be polymerized with catalyst in the presence of loading by oxidizers and fuels. Polymerization of the acrylate will take place at room temperature without catalyst upon standing for a few days, or in bulk or solution with catalyst.

The NF -polyether acrylate thus made has the structural formula:

CH on o o ca =cacoo- 6H2 2 n= 6W l-lgNFg The acrylation of the NF -polyether is performed with an excess of acrylating agent, e.g. acryloyl chloride, from 4:1 to 24:1 stoichiometric excess. ZnCl may be used as catalyst instead of Cu Cl for faster and more complete acrylation, as in the following typical preparation using the components:

2.78 g. (.0012 m.) poly-bis-(NF )-pentene-1 oxide;

4.56 g. (.0504 m.) acryloyl chloride (0.1% Cu Cl polym erization inhibitor);

10 ml. acetonitrile (Eastman 488-dry grade);

0.011 g. ZnCl powdered anhydrous.

The mixture of the above components is heated under N for 3 hours at 50 C. The infrared spectra showed that the OH content has been reduced to 0.01 to 10% of its initial value and ester has appeared. The NF -polyether Example 3 NF -polyether acrylate is made by acrylating with a trifluoroacetic anhydride-acrylic acid mixture containing the components:

.64 g. (.0008 mole) of H 0 modified by poly-bis-(NF pentene-l oxide (800 mol wt.);

4.2 g. trifluoroacetic anhydride (0.2 mole);

1.4 g. acrylic acid (.0195 mole).

This anhydride was added to the acid at 20 C., 15 mins. The flask was then cooled to 0 C. by ice bath and the polyether was added in 2 ml. of CH Cl over 15 mins. at 0 C. Stir at 0 C. for 30 mins. Add 30 ml. ice water and stir for 15 mins. Extract with CH CI wash with NaHCO (saturated) solution 2-5 times, and then distilled water twice. Dry with Na SO (anhydrous), filter and store in solution at 20 C. under air.

Washing the polyether acrylates improves the stability of the final polyacrylate.

A suitable method found for storing the acrylates up until the time they are to be further polymerized in making a rocket propellant composite comprises dissolving the NF -polyether acrylate with the CH CI to form a dilute solution under N or air with a small amount of polymerization inhibitor, 0.01 wt. percent of 2,3-dicyano- 1,4-benzoquinone, and maintaining the solution containing the inhibitor at a low temperature, e.g. 24 C. The NF -polyether acrylate, particularly if it is not well purified, is unstable and tends in air and at room temperature storage to form a sticky and weak polyacrylate when final polymerization is attempted. The final polymerization of the acrylates is intended to form a tough, rubbery product of high tensile strength.

POLYMERIZATION OF NF -POLYETHER ACRYLATES The polymerization of the NF -polyether acrylates is intended to yield and has yielded crosslinked rubbers of good strength. Studies have shown that the crosslinked rubbers are insoluble in many ordinary solvents, and that any of the material which is soluble, such as formed in 6 unsuccessful polymerizations, are low molecular Weight. the polyether through the addition of NF groups. The The satisfactory rubbery polymers are insoluble in resulting NF -polyether is then acrylated in the manner tetrakis-(NF )-furan, tetrakis-(NF butane, acetone, which has been described. CH CN, benzene, CH Cl (ll- C1 CCl and H 0, leav- The acrylate of the poly (divinyl ethylene oxide-N 1 ing little doubt that they are appreciably crosslinked. 5 adduct) is characterized by the unit composition For the polymerization, many of a variety of polym- [C6H8(NF2)4O] erization initiators may be used. Suitable initiators are represented by azoisobutyronitrile, 2,4-dichlorobenzoyl peroxide, and benzoyl peroxide. These initiators are used and is represented by the following structure:

in concentrations of about 0.1 to 1 wt. percent and the 10 2 2 polymerization is carried out at temperatures usually of CHNFQ about 25 to 75 C., the polymerization being completed 1 Q in about 10 to 16 hours to obtain tough, tacky, rubbery H polymel.s CH2=CHCOO 1 0 ccn=cn The polymerization can be carried out with the NF i polyether acrylate dissolved in any of the solvents, such CHNF as the liquid (NF butane, benzene, CH CN, or the halogenated hydrocarbons, or mixtures of such solvents, Q Q n and with the use of the polymerization initiators as mentioned. The polymerization may be carried out under 20 vacuum or in an inert atmosphere, such as N The time of cure varies with the initiator and temperature. During [C H O(NF )O] the polymerization, other crosslinking agents may be used for crosslinking the polyacrylates in the absence of or in the presence of loading, for example, ethylene dia- The acrylate of the N 1 adduct of polybutadiene oxide is characterized by the unit composition and is represented by the structure:

crylate, tetramethyl diacrylate, to give more strength and o O rigidity. For chain extension of the NF -polyether CH =CHCOO on n acrylates, they can be copolymerized with other acrylates CCH=CH that may contain NF e.g. bis-(NFQ-propyl acrylate, or F one with the other. Inspections on the polymerized NF CHQNF polyether acrylates are given in the following table. 2 n

TABLE II.POLY (NFQ-POLYETHER ACRYLA'IES) PPMOA Acrylate 1 Ethylene Glycol Properties Water Modified Modified Glycidol Copolymer Clear brown Clear brown Clear amber.

Appearance.

Consistency. Tough, tacky rubber.-.. Tough, tacky rubben..- Tough, tacky rubber. Gel Fraction .791 782 5.

Tensile Strength, p.s.i. 181 (avg. of 7).... 133 (avg. of 3).

Max Tensile, p.s.i. 222 2 145.

Elongation at Break, percent 3 135 (avg. of 7).. 104 (av g. of 2). Vac. Therm. Stab, 90 C. in ml. of gas/g. at hrs 25.8. 148 (extrapolated). DTA Exotherrn, CA 152 154.

Impact Sens, Kg. In. (Smoke)...

1 Washed, acrylated polyether cured with 0.3 wt. percent AIBN at C. for 15 hours under N 2 Wt. insoluble /wt. total after 24 hour soxhlct extraction with 01-1101 As in 1 cast in a thin film on a. glass plate, pulled as a film. 4 Diflerent thermal analysis.

FORMULATIONS WITH POLY (NF -POLYETHER It will be noted that in the illustrative structures, it is AC-RYLATES) possible for a number n of the polyether groups, in-

dicated by the recurring unit, to be joined to the terminal Test loadlngs of the NF -polyether acrylates with variacrylate or acryloyl groups which contain double bonds ous liquid oxidizers, solid oxidizers, and fuels were made, 50 through which further polymfirizafion can take place so and after polymerization and curing of the hinder, the as to form polyacrylates The polyether chains may be of Solid rocks? propellant Composites Were t ested for physi various molecular weight, depending on the consistency cal P P AS an example; test bars In the Shape of desired for final formulation or use. With high-energy dumbbens were made by loadmg the NFTPOh/ether acry' plasticizers, higher molecular weight NF -po1yether acryl h 80 j t ammonium PerFhlOrate then lates of higher viscosity may be used to prevent settling mg durlng Polymenzatlon a mold Whlch Compressed the of solid components from the composite before or during bars at about 5000 p.s.i. The loaded binder Was found to casting and curing. have gOOd tensfle Strengths abov 250 The NF -polyether acrylates and their polymers have Other test formulations have contained 10 to 30 wt. been made to Contain 49 and more Wt percent N122 The percent of the NF -polyether acrylate mixed with 10 to ol mers of thist which 0 ta 1 NF b d 35 wt. percent of tetrak1s-(N-F )furan or tetrak1s-(NF p y ype c n m ass 2 can e ma 6 but are not as attractive for use as a hlgh-energy oxidizer butane, 30 to wt. percent of ammonium perchlorate binden fines, 4 t0 6 f Percent of boron P K 9 The acrylates of the NF -polyethers given in the order P6110611? alqmmum Powder, Polymenzanon lmtlator of preference with respect to NF and energy content are for curing 1n the manner described. shown in the f ll i table Steps used in preparing the NF -polyether acrylates and polymers of these acrylates which have been de- TABLE III scribed in detail with reference to poly (bis-(NF )-pen- NF? percent by tene-l monoxide) apply also to the acrylates and polyof 2000 3 acrylates made from the N F adduct of polybutadiene NFTpolyether dlacrylate of: dlacrylate (maxlmum) monoxide and N 11 adduct of poly (divinyl ethylene OX- Polydivinylethylene oxide-N Fl adduct ide). In each instance, the unsaturated polyether is formed [C H (NF O) 1,, 64.8 by polymerizing the unsaturated oxide, e.g. divinyl ethyl- Polybutadiene oxide-N 1 adduct ene oxide and butadiene oxide, with an epoxidizing cat- [C H (NF O)] 56.6 alyst such as PF then the resulting unsaturated poly- Polypentadiene oxide-N F adduct ether is reacted with N F to saturate the double bonds in [C H (NF O],, 52.5

The Isp (specific impulse) attainable with even the binder made from the polypentadiene oxide-N 11; adduct diacrylate is in the range of 270 to 285.

It can be easily seen that with a higher ratio of NF groups to carbon, the energy content of the acrylates and polyacrylates of the NF -polyethers increases. For a solid propellant composite containing 20 wt. percent of binder made from diacrylate of [C H O (NF with 20 to 50 Wt. percent C H (N=F as liquid NF oxidizer, 3.5 wt. percent B powder, and 57.5 to- 26.5 wt. percent hydrazinium nitroformate, Isp values determined are in the range of 288 to 290.

Considering the acrylates of the NF -polyethers as described individually or mixed, a general compositional formula for these compounds is represented by:

x y( 2) z 2)v wherein the polyether recurring unit, x is 4 to 6, y is 6 to 8, z is 2 to 4, n is 4 to 50, R is hydrogen or a C to C alkyl substituent in the acryloyl group, and v is 1 to 3.

In addition to the advantages of the physical properties and high-energy content of the polyacrylates formed from the NF -polyethers, the NF -polyether acrylates have the advantages of low heat of polymerization and low shrinkage. These polymerization properties allow a more strainfree large rocket motor to be cast with less tendency for case bonding failure, thermal cracking, voids formation and curing scorch. Low heat of polymerization, i.e. the low amount of abiabatic heat involved during the polymerization, is desirable to minimize decomposition of the polymer and of loading ingredients. As an example, in polymerizing the acrylates of the NF -polyether formed from pentadiene monoxide in the molecular range of 1000 to 3000, the amount of shrinkage during curing is in the range of about 5 to 1 volume percent and decreases with increases in the starting molecular weight of the NF -polyether acrylate. The heat involved during the polymerization of this kind of NF -polyether acrylate also decreases as the molecular Weight is increased and is in the range of about 30 down to about 6 kilocalories per gram for the NEE-polyether acrylate in the range of 1000 to 3000.

It will be understood that the binders made from the NF -polyether acrylates may be modified and crosslinked into complicated three-dimensional structures difficult to depict. In the polymerization, some of the participating NF -polyethers may be monoacrylates, as well as diacrylates and higher acrylates. Also, mixtures of the NF -polyether acrylates formed from different kinds of NF -polyethers may be used for copolymerizations which give chain extension and crosslinking.

The invention described is claimed as follows:

1. Acrylates of NF -containing polyethers having the compositional formula:

wherein the polyether recurring unit, x is 4 to 6, y is 6 to 8, z is 2 to 4, n is 4 to 50, R is of the group consisting of hydrogen and C to C alkyl substituent, and v is 1 to 3, the C H group being a substituted saturated acyclic hydrocarbon group containing the NF substituent groups.

2. Diacrylate of poly (bis-(NF )-pentene-l oxide) having the composition:

n being 4 to 50.

3. Diacrylate of poly (divinyl ethylene oxide-N F adduct) having the composition:

4. Diacrylate of poly (butadiene oxide-N 13; add'uct) having the composition:

nbeing 4 to 50.

5. Rubbery polyacrylates composed principally of the recurring unit:

where x is 4 to 6, y is 6 to 8, z is 2 to 4, v indicates 1 to 2 of the groups for 4 to 50 of the recurring NF -polyether units indicated by subscript n, said units being crosslinked, C H group being a substituted saturated acyclic hydrocarbon group containing the NF substituent groups.

6. Process for preparation of acrylates containing NF groups, which comprises reacting an acrylating agent with an NF -containing polyether alcohol having the composition:

wherexis4to 6,yis6to 8,zis2to4, andnis4to 50, the C H group being a substituted saturated acyclic hydrocarbon group containing the NF substituent groups.

7. Process of claim 6, in which the acrylating agent is acrylic acid.

8. Process of claim 6, in which the acrylating agent is acrylic acid with trifluoroacetic anhydride.

9. Process of claim 6, in which the acrylating agent is acryloyl chloride.

10. Process of claim 6, in which the acrylating agent is acrylic anhydride.

11. Process of claim 6, in which the acrylated polyether is fiurther polymerized and crosslinked to form a rubbery polymer.

12. Copolymers of NF -containing polyether acrylates having a recurring ether unit containing NF groups as the substituent groups in a substituted saturated acyclic hydrocarbon group of 4 to 6 carbon atoms in each recurring ether unit.

13. Copolymers of N-F -containing polyether acrylates defined in claim 12 in which the said acrylates are copoiymerized with a reactant selected from the group consisting of ethylene diacrylate, tetramethyl diacrylate, and bis-(NF )-propyl acrylate.

14. Process for the preparation of poly (NF -polyether acrylates), which comprises reacting an acrylating agent with an NF -containing polyether alcohol selected from the group consisting of poly (bis(NF )-pentene-1- oxide), poly (divinyl ethylene oxide-N F adduct) and poly (butadiene oxide-N F adduct), modified to have about two OH groups per molecule'by a modifying reactant selected from the group consisting of water, glycidol, ethylene glycol and trimethylol propane to replace the OH groups by acrylate groups, and polymerizing the resulting acrylates to form rubbery polymers.

References Cited Farber: Astronautics August 1960, pp. 34, 40 and 42. Hoffman et al.: Chem. Reviews, vol. 62, pp. 12 to 1-8 (1962).

LELAND A. SEBASTIEN, Primary Examiner.

US. Cl. X.R. 

1. ACRYLATES OF NF2-CONTAINING POLYETHERS HAVING THE COMPOSITIONAL FORMULA:
 2. DIACRYLATE OF POLY (BIS-(NF2)-PENTENE-1OXIDE) HAVING THE COMPOSITION:
 3. DIACRYLATE OF POLY (DIVINYL THEYLENE OXIDE-N2F4 ADDUCT) HAVING THE COMPOSITION:
 14. PROCESS FOR THE PREPARATION OF POLY (NF2-POLYETHER ACRYLATES), WHICH COMPRISES REACTING AN ACRYLATING AGENT WITH AN NF2-CONTAINING POLYETHER ALCOHOL SELECTED FROM THE GROUP CONSISTING OF POLY (BIS(NF2)-PENTENE-1 OXIDE), POLY (DIVINYL ETHYLENE OXIDE-N2F4 ADDUCT) AND POLY (BUTADIENE OXIDE-N2F4 ADDUCT), MODIFIED TO HAVE ABOUT TWO OH GROUPS PER MOLECULE BY A MODIFYING REACTANT SELECTED FROM THE GROUP CONSISTINF OF WATER, GLYCIDOL, ETHYLENE GLYCOL AND TRIMETHYLOL PROPANE TO REPLACE THE OH GROUPS BY ACRYLATE GROUPS, AND POLYMERIZING THE RESULTING ACRYLATES TO FOM RUBBERY POLYMERS. 